Iron/iron oxide (Fe/Fe2O3) nanoparticles were deposited on the surface of different carbonaceous anode materials: carbon felt (CF), carbon cloth (CC), and graphite (G) as an effective catalyst to improve the anode performance of microbial fuel cell (MFC) based on the real industrial wastewater. Interestingly, the results of the characterization indicated the novel structure of the iron nanoparticles enveloped with a thin layer of iron oxide formed on the anode surfaces. This novel structure enhances the surface wettability of the electrode, the degradation reactions rate of organic compounds, and the microorganism adhesion on the electrode surface, and decreases the electron transfer resistance. Therefore, the generated power and current were considerable improved, where, the generated power was increased by 385%, 170%, and 130%, for the CF, CC, and G electrodes, respectively. Moreover, the MFC based on the modified electrodes achieved the excellent removal percentage (more than 80%) of organic compounds from wastewaters: This study presents a new approach for MFC application on a large scale based on low-cost and high-efficiency anodes for simultaneous power generation and wastewater treatment.